text:
|Publication number
|Publication type
|Application number
|Publication date
|Jan 4, 1994
|Filing date
|Dec 13, 1991
|Priority date
|Jan 19, 1990
|Fee status
|Also published as
|Publication number
|Gene B. Portelli, William J. Schultz, John T. Boden, Daniel M. Kaufer
|Original Assignee
|Minnesota Mining And Manufacturing Company
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (26), Non-Patent Citations (3), Referenced by (56), Classifications (57), Legal Events (5)
|External Links: USPTO, USPTO Assignment, Espacenet
This is a continuation-in-part of application Ser. No. 07/596,769, filed Oct. 12, 1990, now abandoned, which is a continuation-in-part of application No. 07/467,729, filed Jan. 19, 1990, now abandoned.
The present invention relates to thermosettable resin compositions and their use together with reinforcing filaments in the production of advanced composites.
Thermosettable resins are well known for their use in structural adhesives, in high performance composites, and in prepregs. Composites and prepregs made from these thermosettable resins and high strength fibers such as glass, ceramics, carbon and the like provide articles having considerably less weight than the same article made from metal. The articles, however, made using these thermosettable resins have been brittle, a characteristic that necessarily seriously limits their use. Also, because the viscosity of the thermosettable resins has been either too high during processing or too low during curing many of the articles are rejected because of the development of voids and imperfections in the articles.
Efforts have been made to control the viscosity of the thermosettable resins. Flow control agents, such as fumed silica, clay, whiskers, and high molecular weight polymers, have been added to thermosettable resins. These agents increase the viscosity over all temperature ranges, often making processing difficult or impossible and frequently harm the physical characteristics of the cured article.
High performance thermosetting resins include such resins as epoxies, bismaleimides, and cyanates. These resins react with curing agents or in the presence of polymerization catalysts to yield high performance resins that have gained wide acceptance as protective coatings, electrical insulations, structural adhesives, and as a matrix resin together with reinforcing filaments in advanced composites. Where high glass transition temperatures, thermal resistance, and chemical resistance has been attained by the cured resin, the cured resin has generally had poor physical characteristics and been brittle, had poor impact resistance and fracture properties.
There are many references in the art teaching means for improving physical characteristics of cured thermosetting resins, primarily thermosetting epoxy resins, by use of a particular hardener and/or the addition of another polymer and/or an inorganic particulate material.
References among many others that teach means for improving the physical characteristics of cured thermosetting epoxy resin by the addition of a thermoplastic resin include the following:
U.S. Pat. No. 3,784,433 discloses that composites of unidirectional carbon fibers and a thermosettable resin are made by applying the resin as a continuous film to the carbon fibers, applying heat and pressure so that the resin flows about the fibers and forms a coherent structure, and then converting the resin into its solid, fusible B-stage. Heating cycles can be very short as there is no solvent to evaporate, and the thin layers can be cooled quickly.
U.S. Pat. No. 4,524,181 discloses compositions curable to articles having reduced susceptibility to mechanical and thermal shock comprising an epoxy resin and colloidally dispersed elastomeric particles.
U.S. Pat. No. 4,558,078 discloses compositions useful as a prepreg comprising an epoxy prepolymer and curative and optionally a second resin that can be present homogeneously or in the form of an interpenetrating network.
European Patent Application 0 274 899 discloses a prepreg consisting of a fiber reinforced resin having as a separate phase fine thermoplastic or thermosetting resin particles distributed throughout the prepreg, preferably the particles are localized in the inter-layer zones of the composite material and remain as a separate phase upon curing the prepreg.
In U.S. Pat. No. 4157,360 there is disclosed melts of dicyanates and thermoplastic polymers and in U.S. Pat. Nos. 4,745,215 and 4,780,507, there are disclosed blends of dicyanates and thermosetting or thermoplastic polymers. In European Patent Application 0 301 361 there are described rubber-modified cyanate ester resins and polytriazines derived therefrom and in U.S. Pat. No. 4,804,740 there are described curable cyanate ester formulations containing thermoplastics. In U.S. Pat. No. 4,468,497, there is disclosed bis-imides, crosslinking agents, and compatible elastomers; the compositions of these references being useful for making prepregs.
M. T. Blair et al. at the 33rd International SAMPE Symposium of Mar. 7-10, 1988, presented a paper titled "The Toughening Effects of PBI in a BMI Matrix Resin" in which they disclosed the dispersion of 10% polybenzimidazole into a blend of bismaleimide and o,o'-diallylbisphenol A. Such a composition would not exhibit a "dissolution temperature" required in the composition of the instant invention.
Briefly, the present invention provides a thermosettable resin composition having a viscosity at temperatures used for processing and compounding similar to the viscosity of the unmodified thermosetting resin but having a significant increase in viscosity at higher resin temperatures up to the curing temperature. The thermosettable resin composition comprises a thermosettable resin mixture, which is a liquid at a temperature in the range of 20� to 100� C., comprising:
a) one or more thermosettable resins and one or more of curatives, hardeners, and catalysts for the thermosettable resin in an amount sufficient for cure of the thermosettable resin, and
b) 2 to 50, preferably 2 to 30, parts per 100 parts of thermosettable mixture, of resin particles of one or more amorphous thermoplastic polymers having a Tg of 140� C. or higher, the particles having a dissolution temperature (defined hereinafter) of 50� C. or higher, preferably 70� or higher, and the particles being essentially insoluble in the thermosettable resin at temperatures up to about 15� C. below the dissolution temperature. The composition may optionally contain additives for property enhancement.
The invention also provides prepregs for structural composites comprising a web of fibrous material impregnated with the thermosettable composition of the invention.
As used in this application:
"dissolution temperature" ("Td ") means the temperature at which the viscosity of a composition of thermosettable resin and thermoplastic particles in the absence of curatives, hardeners, or catalyst for the thermosettable resin, when raised at a rate of about 2� C per minute, reaches a minimum value and then begins to rise as the thermoplastic particles begin to dissolve. This is the temperature at which the thermoplastic particles begin to dissolve; and
"temperature of complete dissolution" "Tdc " represents the temperature at which the thermoplastic particles are completely dissolved in the thermosettable resin when the temperature is raised at a rate of about 2 degrees Centigrade per minute.
Means disclosed in the background art for solving physical shortcomings of the cured thermosetting resin have not solved problems arising in processing of thermosetting resins into useful articles. In processing of a thermosetting resin composition into an article such as a prepreg that can be used in the manufacture of composite structures, the viscosity profile of the thermosetting resin composition is very important. It is important that the viscosity of the composition be relatively low during compounding, coating and impregnating of a fiber reinforcement but becomes relatively high before the final cure temperature during the curing process to allow the application of vacuum to remove volatiles and the application of pressure to shape the composite part without bleeding of excessive amounts of resin that would cause voids and imperfections in the cured composite part.
Aspects of the invention which are capable of illustration are shown in the accompanying drawing wherein graphs show the relationship of viscosity to temperature for compositions according to the invention and for state-of-the-art compositions.
In the drawing, FIG. 1 (details of the formulation and procedures are given in Example 1, below), curve A (comparative) represents the viscosity profile for a conventional thermosetting resin. As can be seen, the viscosity decreases with increasing temperature. Curve B (comparative) is the viscosity profile for a composition of the thermosetting resin of Curve A and 8.5% by weight of polyetherimide thermoplastic. For this trial the thermoplastic has been completely dissolved into the thermoset during mixing to form a completely homogeneous blend. This formulation exhibits a viscosity profile which is well above the unmodified thermosetting resin over all temperature ranges. The formulation of curve C (present invention) is identical to that of curve B, however, in this trial, the polyetherimide thermoplastic is in particle form and is mixed into the thermoset to form a dispersion where none of the thermoplastic is dissolved. The viscosity profile obtained is unique in that, the initial viscosity is essentially the same as that for curve A. However, after the first minimum in viscosity occurs, which is the dissolution temperature (Td), the thermoplastic particles dissolve. This raises the viscosity of the composition up to the level obtained for the homogeneous blend of Curve B.
In FIG. 2 of the drawing, curve D shows a viscosity profile for a composition (i.e., Example 3, formulation 0), of the invention. Points I, II, and III represent Td (106� C.) Tdc (120� C.) and cure temperature (177� C.), respectively. Curve E shows the temperature profile for the composition of curve D.
Thermosetting resins that can be used as component (a) in the composition of the invention are epoxy, N,N'-bismaleimide, and polycyanate monomers and prepolymers that are liquid at a processing temperature and can be cured to a thermoset resin composition at a temperature of 100� C. or higher.
Epoxy monomers and prepolymers that can be used in the compositions of the invention are well known and most are commercially available. They are compounds in which there is present at least an aromatic or cycloaliphatic ring structure and one or more epoxy groups, e.g., ##STR1## Compounds having more than one epoxy group are preferred. Aromatic polyepoxides, the most preferred epoxy compounds, are the polyglycidyl ethers of polyhydric phenols, glycidyl esters of aromatic carboxylic acid, and polyglycidyl derivatives of aromatic amines such as N-glycidylaminobenzene, and glycidylamino-glycidyloxybenzenes.
Examples of aromatic polyepoxides, useful in the thermosettable resin composition of the invention, include the polyglycidyl derivatives of polyhydric phenols such as 2,2-bis[4-(2,3-epoxypropoxy)phenyl]propane and those described in U.S. Pat. Nos. 3,018,262 and 3,298,998, incorporated herein by reference and in "Handbook of Epoxy Resins" by Lee and Neville, McGraw-Hill Book Co., New York (1967). A preferred class of poly(glycidyl ether)s of polyhydric phenols of use in the compositions of the invention are the diglycidyl ethers of bisphenols that have pendent carbocyclic groups such as those described in U.S. Pat. No. 3,298,998, which is incorporated herein by reference. Examples of such diglycidyl ethers are 2,2-bis[4-(2,3-epoxypropoxy)phenyl]norcamphane, 9,9-bis[4-(2,3-epoxy-propoxy)phenyl]fluorene, and 2,2-bis[4-(2,3-epoxypropoxy)phenyl]decahydro-1,4,5,8-dimethanonaphthalene. A much preferred diglycidyl ether is diglycidyl ether of bisphenol A.
Examples of N-glycidylaminobenzenes suitable for use in the epoxy resin composition of the invention include the di and polyglycidyl derivatives of benzenamine, benzene diamines, naphthylenamine and naphthylene diamine such as N,N-diglycidylbenzenamine, N,N-diglycidylnaphthalenamine [given the name of N-1-naphthalenyl-N-(oxiranylmethyl)oxiranemethanamine by Chemical Abstracts 9th Coll. Index, Vol. 76-85, page 2660 CS (1972-76), 1,4-bis(N-glycidylamino)benzene, 1,3-bis(N,N-diglycidylamino)benzene, and bis[4-(diglycidylamino)phenyl]methane (MY 720™, Ciba Geigy, Inc.). The polyglycidyl derivatives of aromatic aminophenols are described in U.S. Pat. No. 2,951,825. An example of these compounds is N,N-diglycidyl-4-glycidyloxybenzenamine (ERL 0510™, Ciba Geigy, Inc.).
When component (a) of the composition of the invention contains an epoxy monomer or prepolymer it can be cured by a variety of curing agents as are known in the art, some of which are described, together with the method for calculating the amount to be used, in the book by Lee and Neville, "Epoxy Resins," pages 36 to 140, McGraw-Hill Book Company, New York, 1957. Useful curing agents include polyamines such as ethylenediamine, diethylenetriamine, aminoethylethanolamine, and the like, diaminodiphenylsulfone, 9,9-bis(4-aminophenyl)fluorene, 2,7-dichloro-9,9-bis(4-aminophenyl)fluorene, an amide such as dicyandiamide, polycarboxylic acids such as adipic acid, and acid anhydrides such as phthalic anhydride and chlorendic anhydride, and polyphenols such as bisphenol A, and the like. The curing agent is chosen such that very little if any polymerization of the epoxy takes place under about 100� C. but does take place with increasing rapidity as the temperature is increased above about 125� C. Generally, the epoxy composition and curing agent are used in stoichiometric amounts. However, the curing agent can be used in amounts ranging from about 0.1 to 1.5 times the stoichiometric amount of epoxy resin.
Thermally activated catalytic agents may also be used, e.g., Lewis acids and bases, tertiary amines, imidazoles, complexed Lewis acids, and organometallic compounds and salts, such as the BF3 -amine complexes, SbF5, and benzyldimethylamine. When a thermally activated catalyst is included, about 0.01 to 5 percent by weight of catalyst, based on the amount of epoxy compound present in the thermosettable resin composition, is used.
N,N'-bismaleimide monomers and prepolymers that can be used in the composition of the invention are also well known, many of which can be purchased commercially. They are compounds in which there is present at least one, preferably two, maleimido groups and have general formula I: ##STR2## where Y represents an alkylene group of at least 2 carbon atoms, preferably 2 to 6 carbon atoms, and Z is a divalent organic group containing at least 2 carbon atoms and generally no more than 20 carbon atoms. Z may be aliphatic, cycloaliphatic, aromatic or heterocyclic, these groups optionally having up to two of each of sulfur and non-peroxidic oxygen heteroatoms. Y may be derived from dicarboxylic acids or anhydrides such as maleic, citraconic, tetrahydrophthalic, and the like.
Representative N,N'-bis-imides that may be employed are the N,N'bismaleimides of 1,2-ethanediamine, 1,6-hexanediamine, trimethyl-1,6-hexanediamine, 1,4-benzenediamine, 4,4'-methylenebisbenzenamine, 2-methyl-1,4-benzenediamine, 3,3'-methylenebisbenzenamine, 3,3'sulfonylbisbenzenamine, 4,4'-sulfonylbisbenzenamine, 3,3'oxybisbenzenamine, 4,4'oxybisbenzenamine, 4,4'-methylenebiscyclohexanamine, 1,3-benzenedimethanamine, 1,4-benzenedimethanamine, and 4,4'-cyclohexanebisbenzenamine and mixtures thereof. Other N,N'bis-maleimides and their process of preparation are disclosed in U.S. Pat. Nos. 3,562,223, 3,627,780 and 3,839,358, the disclosures of which are incorporated herein by reference.
The preparation of the N,N'-bismaleimides is well known and described in U.S. Pat. No. 4,468,497 which is incorporated herein by reference for that purpose.
The N,N'-bismaleimides are polymerized by heating them together with a diamine into which they can be dissolved at temperatures of 100� C. or lower and optionally a diunsaturated crosslinking agent.
Diamines that can be used in polymerizing the N,N'-bismaleimides are described in U.S. Pat. No. 3,562,223, which is incorporated herein by reference for that purpose. Preferred diamines which may be employed are diamines having a cycloalkyl or aryl group, and are the same as those listed above, that are of use in the preparation of the N,N'-bismaleimides.
Generally, from about 0.2 to 0.8 moles of diamine are used per mole of N,N'-bismaleimide.
Diunsaturated cross-linking agents of use in the N,N'-bismaleimide compositions of the invention are any diunsaturated compounds having a boiling point at atmospheric pressure of about 150� C. or higher and terminal ethylenic unsaturation. Preferred cross-linking agents are divinylbenzene, diallyl phthalate, and bis(4-allyloxyphenyl)ether.
Dicyanate monomers and prepolymers that can be used in the composition of the invention are also well known. References to their preparation and use in polycyclotrimerization to produce polycyanurates are described in U.S. Pat. No. 4,157,360 which is incorporated herein by reference. The dicyanates are compounds having general formula II:
N.tbd.CO--R--OC.tbd.N II
wherein R is a divalent aromatic hydrocarbon residue and comprises at least one aromatic moiety, i.e., aromatic ring including benzene, naphthalene, anthracene, phenanthrene and the like, and where R contains a total of up to 40 carbon atoms, including the aromatic moiety. For example, R can be 1,4-di(2'-phenylpropyl)benzene moiety, to which the cyanate groups are attached in the para positions of the benzene rings of the phenylpropane substitutents to provide one embodiment of compounds of formula II. The aromatic rings of R may be further substituted with groups that are inert during the polymerization process, i.e., the polycyclotrimerization process, and include halogen, including fluorine, chlorine, bromine, and iodine; C1 -C4 alkoxy, being linear or branched and including methoxy, ethoxy, isopropoxy, and t-butoxy; and C1 -C4 alkyl carbonyloxy group, being linear or branched, including methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl and t-butoxycarbonyl; wherein the number of substitutents on the aromatic rings may be one or more with the proviso that the groups are inert during the polymerization process and do not substantially interfere with the formation of the crosslinked triazine polymer upon polycyclotritrimerizing of the aromatic dicyanate moiety.
By the term "polycyclotrimerization" is meant forming a cyanurate ring system by the polymeric condensation of three aromatic cyanate groups to form a crosslinked aromatic ring system, which has as its basic repeating unit the group of formula III: ##STR3## in which R substituents, independently as defined above, are attached to oxygen atoms. Methods for conducting the polymerization are well known, including thermal annealing above about 200� C. and are described in the Korshak reference discussed in U.S. Pat. No. 4,157,360, cited above.
Preferred dicyanates are those in which R in Formula III can have any of the structural formulae: ##STR4## or combinations thereof.
When polycyanates are used in component (a) of the composition of the invention, mixtures of any proportions of polycyanates and prepolymers of the polycyanates and optionally monocyanates that are liquid at the processing temperature which preferably is in the range of 20� to 100� C. can be used. Prepolymers are made by heating the blends with or without catalyst at a temperature of about 140� C. to about 220� C. for a time sufficient to cyclotrimerize from about 5 to about 50 percent of the cyanate functional
Catalysts that can be used in cyclotrimerizing the polycyanates to form prepolymers and completely polymerized polycyanurates include zinc octoate, tin octoate, zinc stearate, tin stearate, copper acetylacetonate, phenol, catechol, triethylendiamine and chelates of iron, cobalt, zinc, copper, manganese and titanium with bidentate liquids such as catechol. Such catalysts are used in the amounts of about 0.001 to about 20 parts by weight per 100 parts of the polycyanate ester blend. Other catalysts and their use in curing polycyanates are disclosed in Great Britain Patent No. 1,305,762 incorporated herein by reference. It is, however, possible to conduct the formation of prepolymers and the complete polymerization without a catalyst, utilizing only heat.
Cyanate esters that can be used include RDX 80352™ a prepolymer of bisphenol A dicyanate, by Interez, Inc; XU71787™ a polycyanate of a polyphenol adduct of dicyclopentadiene by Dow Chemical Company; and BT 2160™ resin, a prepolymer of bisphenol A dicyanate containing 10% by weight of 4,4'-methylenedianiline bismaleimide, commercially available from Mitsubishi Gas Chemical Company.
Resin particles which can be used as component (b) in the thermosettable resin composition of the invention have a dissolution temperature above about 50� C., preferably above about 70� C., and are insoluble in the thermosettable resin at temperatures up to about 15� C. below the dissolution temperature but soluble at a temperature below the onset of curing which varies depending on the resin but generally is in the range of 100� to 200� C.
The resin particles are prepared from amorphous thermoplastic resins having a glass transition temperature above about 140� C. Resin particles having the required solubility characteristics have a solubility in the thermosettable resin that is low enough to prevent the particles from dissolving when the particles are mixed into the thermosettable resin or during storage of the thermosettable mixture. The resin particles, however, also have a solubility sufficient to allow the particles to be completely dissolved in the thermosettable resin during the cure cycle of the composition. The resin particles dissolve at a temperature below the cure temperature by at least 20� C., preferably by at least 24� C., to form a homogeneous solution.
Thermoplastic resins suitable for preparation of the resin particles of the invention are amorphous thermoplastics including polycarbonates, polysulfones, polyarylates, polyethersulfones, polyarylsulfones, polyesters, polyetherimides, polyamideimides, polyimides, polyamides, and polyethers. Preferred thermoplastic resins are polyetherimides such as ULTEM™ 1000, available from General Electric polyethersulfone, such as Victrex™ 4800P, available from ICI, and polyarylsulfone, such as Radel™ A-200 available from Amoco. The suitability of a particular thermoplastic resin is dependent on meeting the above solubility characteristics in the specific thermosettable resin being used in the thermosettable resin composition.
The resin particles having the desired solubility characteristics can be prepared by a variety of well know techniques, including techniques such as grinding of the solid amorphous thermoplastic resin, spray drying of solutions of the amorphous thermoplastic resin, or coagulation of emulsions of the amorphous thermoplastic resin. Suitable particles preferably have a surface area of at least 0.5 square meter per gram and most preferably a surface area of 1.0 m2 /g or greater. Average particle sizes generally are in the range of 0.5 to 50 micrometers, preferably 0.5 to 40 micrometers. More preferably fully densified particles are in the range of 0.5 to 10 micrometers and porous particles are in the range of 0.5 to 40 micrometers.
The surface area of the amorphous resin particle is important. The surface area of the particle controls the dissolution rate of the thermoplastic particle into the thermosetting resin to form a homogeneous solution. If the surface area is too low the dissolution rate is slow and can result in the thermosetting resin curing before the particle can dissolve. If the particle does not dissolve prior to curing the desirable enhanced viscosity will not be imparted. The high surface area of particles useful in the present invention enables the particles to fully dissolve, forming a homogeneous solution in the resin mixture prior to cure, and preferably providing a homogeneous cured network.
Particles having high surface area can be prepared in several ways. A small particle has a high surface area. These particles can be prepared by grinding or coagulation of a polymer dispersion. Another method of obtaining a high surface area is to prepare porous particles. Porous particles can be obtained by spray drying solutions of amorphous thermoplastics, as is known in the art.
The solubility characteristics of a particular resin particle can be adjusted, i.e., the dissolution temperature lowered, by the incorporation of a plasticizer, i.e., from about 5 to 50 percent by weight, into the thermoplastic resin from which the resin particle is prepared. Preferably, the plasticizer has a functional group that will copolymerize with the thermosettable resin, i.e. a reactive plasticizer. As examples, an epoxy resin, for example the diglycidyl ether of bisphenol A, can be used to plasticize a particle to lower its dissolution temperature, i.e., increase its rate of dissolution into an epoxy resin or a cyanate resin composition. For example, an amine can be used to plasticize a particle to increase its rate of dissolution into N,N'-bismaleimide monomers and prepolymers.
By the phrase "essentially insoluble", it is meant that generally less than about 25% of the particles dissolve when the composition is held at a temperature of 15� C. less than the dissolution temperature for at least two hours, such that the viscosity of a composition of the thermoplastic particles in the thermosettable resin does not change significantly, i.e., to a point making processability difficult.
The thermosettable compositions of the invention are suitable for use as impregnating, laminating or molding resins. They can be used as sealants, insulating materials and adhesives. They are particularly suitable for use in prepregs for the production of space age reinforced composite structures.
The thermosettable resin composition of the invention can be used to impregnate woven or non-woven webs, filaments, rovings or the like at a temperature below the dissolution temperature in the preparation of prepregs. Fibers that can be used in such prepregs include organic and inorganic fibers including, for example, glass fibers, carbon or graphite fibers, ceramic fibers, boron fibers, silicon carbide fibers, polyimide fibers and the like, and mixtures thereof. The thermosettable composition of the invention can also be used to coat woven and non-woven webs, films and foils of organic and inorganic materials including, for example, such organic materials as polyolefins, polyesters, polyimide, and the like and inorganic materials such as ceramics, copper, and nickel, and gold. These materials can be useful in printed circuit technology and as structural components for machinery.
The composition of the invention can also contain additives to modify characteristics of the cured composition. Additives among others that can be used include: inert fillers, tougheners, whiskers, pigments, dyes and flame retardants such as, for example, chopped fibers such as ceramic fibers, glass fibers, boron fibers, carbon fibers, and their woven and nonwoven fabrics; inorganic powders such as kaolin, chalk, silica, antimony trioxide, titanium oxide, carbon; and solid microspheres of glass, ceramic, and metal.
The thermosettable compositions of the invention are prepared by dispersion of the thermoplastic particles, curatives, hardeners, catalysts, and modifying additives into the thermosettable resin at a temperature at which the thermosettable resin is liquid, generally at about 30� to 60� C. but below the dissolution temperature of the particle in the thermosettable resin. The dispersion of the particles into the thermosettable resin is generally accomplished by conventional high shear mixing devices, such as by use of a planetary mixer, kneader, vacuum mixer, ball mill, paint mill or high speed stirrer. When the mixed composition is then maintained at a temperature of 15� C. or more below the dissolution temperature, the composition is stable against gelling for two hours or longer.
More particularly, in a preferred embodiment, the invention provides a process for preparing a thermosettable composition comprising the steps of:
dispersing thermoplastic particles having a surface area of at least 1.0 m2 /g into a thermosettable resin at a temperature at least 15� C. below the dissolution temperature of the particles in the thermosettable resin,
increasing the temperature at a rate sufficient to effect complete dissolution of the particles and provide a homogeneous solution of the particles in the thermosettable resin, the temperature of complete dissolution of the particles being at least 20� C. below the cure temperature of the resin,
continuing to increase the temperature so as to effect cure of the homogenous solution to provide a cured thermosettable composition, which preferably is a homogeneous cured thermosettable composition.
While these thermosettable compositions of the invention are generally processed by hot melt coating techniques, organic solvents such as methyl ethyl ketone, toluene, tetrahydrofuran, ethyl acetate, ethyl alcohol, etc., can also be used to process these resin compositions. For example, solvent processing may be desirable to prepare a thin adhesive film from these thermosettable compositions. When solvents are used care must be used to select a solvent that will dissolve the liquid thermosetting resin but will not dissolve the thermoplastic particle. Suitable substrates for coating the compositions of the invention include sheets and foils of polyimide, polyester, polyolefin, metal, and the like, and fibers such as carbon, glass, aramide, ceramic, and the like.
The invention also provides a process for preparing an uncured prepreg comprising the steps of:
providing at least one layer of a composition comprising dispersed thermoplastic particles having a surface area of at least 1.0 m2 /g in a thermosettable resin at a temperature at least 15� C. below the dissolution temperature of the particles in the thermosettable resin,
laminating said at least one layer to reinforcing fibers at a temperature at least 15� C. below the dissolution temperature of the particles to form a prepreg,
heating said prepreg at a rate sufficient to effect complete dissolution of the particles in the resin and provide a homogeneous solution of the particles in the thermosettable resin, the temperature of complete dissolution of the particles being at least 20� C. below the cure temperature of the resin to form a composite article, and continuing to heat the composite article so as to form a cured composite article.
Objects and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention. In the examples all parts and percentages are by weight and temperatures are in degrees centigrade unless otherwise noted.
In the examples which follow, the viscosity profiles were obtained using an RDA-700™ Dynamic Mechanical Analyzer (Rheometrics, Inc.). The instrument was used in the parallel-plate mode under the following conditions: gap=1 mm, radius=19.02 mm, frequency=100 rad/sec, strain=20%, temperature ramp at 2� C./min, initial temperature=50� C., and final temperature=177� C., which was the cure temperature.
A thermosettable resin composition was prepared by mixing 35 parts of 9,9-bis[4-(2,3-epoxypropoxy)phenyl]fluorene (DGF) and 65 parts of diglycidyl ether of bisphenol A (DGEBA). The resin composition was then used in three formulations: into Formulation A, no additional material was added; into Formulation C, 8.5% by weight of a particulate PEI (ULTEM resin, a polyetherimide resin available from General Electric) having a particle size of 3.2 microns and a surface area of about 5.4 m2 /g was dispersed into the resin composition at 60� C. using an air stirrer; Formulation B was the same as Formulation C, however the mixture was heated to 120� C. and stirred to allow the thermoplastic ULTEM to completely dissolve into the resin composition. The viscosity profile of each formulation was determined using the RDA-700 Dynamic Mechanical Analyzer described above and plotted in FIG. 1. Curve A, for unmodified resin composition shows a steady decrease in viscosity as the temperature of the composition is increased. Curve C, for the resin composition modified with particulate thermoplastic, shows about the same decrease in viscosity of the mixture as for the unmodified resin composition as the temperature is increased up to the dissolution temperature, Td, where the thermoplastic begins to dissolve. At this temperature the viscosity increase, due to the dissolving thermoplastic particles, offsets the viscosity decrease of the resin composition alone and prevents further decrease in the viscosity of the mixture. Curve B, for the resin composition modified with dissolved thermoplastic shows an initial viscosity much higher than the viscosity of the composition modified with particulate thermoplastic. Formulation C thus provides the low viscosities desirable at the initial temperatures of a processing operation, e.g., prepreg fabrication, and the higher viscosities (i.e., controlled flow) that are advantageous at cure temperatures to insure void-free cured composites.
Thermosettable resin compositions were prepared as shown in Table I.
TABLE I______________________________________CompositionFormu- Thermo- % Thermo- Minimumla- settable plastic Viscositytion Resin particle.sup.(d) Td �C. Tdc �C. (poise)______________________________________D (a) None (e) 0.36E (a) 8.5 115 137� C. 4.78F (b) None (e) 0.15G (b) 8.5 119 135� C. 2.55H (c) None (e) 1.20I (c) 8.5 115 124� C. 10.60______________________________________ (a) Thermosettable resin is 100 parts of 4,4tetraglycidyldiaminodiphenylmethane (TGDDM) and 31 parts of 4,4diaminodiphenylsulfone (DDS) mixed at 120� C. with an air stirrer to completely dissolve the DDS. (b) Thermosettable resin is AroCy B30 ™, a dicyanate available from HiTek Polymers, Inc. (c) Thermosettable resin is Compimide ™, a bismaleimide resin availabl from Shell Chemical Co. (d) PEI thermoplastic particle (disclosed in Example No. 1). (e) Thermosettable resin without the thermoplastic particle dose not reveal a dissolution temperature, Td.
Viscosity profiles of each formulation was determined using the RDA-700 Dynamic Mechanical Analyzer and the dissolution temperature, Td, and minimum viscosity of each recorded in Table I. Each of the thermosettable resins, an epoxy, a dicyanate, and a bismaleimide show minimum viscosities of 0.36, 0.15, and 1.20 poise, respectively while these thermosettable resins to which 8.5% by weight of thermoplastic particulate resin have been added show a dissolution temperature of 115�, 119�, and 115�, respectively, and a corresponding minimum viscosity of 4.78, 2.55, and 10.60 poise, respectively.
Thermosettable compositions of a fluorene epoxy resin PR-500 (3M), with various thermoplastic resins were prepared by mixing 4.65 parts of each thermoplastic resin shown in Table II with 50 parts of PR-500 at 60� C. using an air stirrer. The viscosity profile of each mixture as well as that of the composition without added particulate thermoplastic was obtained and minimum viscosity and dissolution temperature of each recorded in Table II.
TABLE II______________________________________CompositionFormu- Thermo- % Thermo- Minimumla- settable plastic Viscositytion Resin particle (Tg)1 Td �C. Tdc �C. (poise)______________________________________J PR-500f None (e) 0.30K PR-500f PESg (230) 119 137� C. 1.61L PR-500f PCh (154) 74 92 2.34M PR-500f PSi (190) 86 108 6.50N PR-500f PASj (220) 106 123 3.76 O* PR-500f PEIk (217) 106 128 9.30P PR-500f 50 PAS/50PEI 106 125 4.15Q PR-500f FPEm (330) 105 133 2.80______________________________________ *Graph D represents viscosity profile data of Formulation O. Data points represent viscosity of the composition as temperature was raised 2.degree C. every 1 minute. e no dissolution temperature observed f an aromatic epoxy resin available from 3M g Victrex 4800 ™, a polyethersulfone available from ICI Americas, Inc. h Lexan ™, a polycarbonate available from General Electric Co. i Udel ™ P1700, a polysulfone available from Amoco Performance Products, Inc. j Radel ™ A200, a polyarylsulfone available from Amoco Performanc Products, Inc. k Ultem ™ 1000, a polyetherimide available from General Electric Company l The glass transition temperature of the thermoplastic resin m A polyester resin prepared from a fluorene bisphenol and isophthalic/terephthalic acid (a 50/50 mol ratio)
The data of Table II show that on heating an unmodified epoxy resin, Formula J, that the viscosity dropped to a minimum of 0.30 poise while for epoxy resin modified by a variety of thermoplastic particles that were soluble at a dissolution temperature, Td, and essentially insoluble below this temperature, the viscosity of the composition does not drop below a much higher value depending on the particular thermoplastic.
Portions of Formulation J and Formulation O of Example 3 were degassed and cured in molds at 177� C. for four hours. Fracture toughness, KIC (critical plane-strain fracture toughness in Mode I), and Tensile Modulus for each cured sample were determined following the procedures of ASTM E399-83 and ASTM D638-86, respectively. Values obtained are recorded in Table II.
TABLE III______________________________________Composition Thermo-Formu- settable Thermoplastic KIC Tensilelation Resin Particle MPa-m1/2 Modulus GPa______________________________________J PR-500 None 0.644 3.52O PR-500 8.5% PEI 0.909 3.42______________________________________
As the data of Table III illustrates, the addition of thermoplastic particles, PEI, that began to dissolve at a dissolution temperature but were essentially insoluble below this temperature, provided an increase of about 44% in the fracture toughness of cured resin with essentially no loss in the tensile modulus.
A formulation of PR-500 epoxy resin and 8.5% by weight of PEI particles was examined in an RDA-700 Dynamic Mechanical Analyzer as described above with the exception that the temperature was elevated at 2� C. per minute until the temperature of the formulation reached 70� whereon the temperature was held at 70� C. for a two hour dwell. The viscosity of the formulation remained unchanged during this dwell time. Upon raising the temperature, the characteristic Td was seen and the viscosity of the formulation increased.
Illustrating control of dissolution temperature by control of the surface area of the thermoplastic particle.
Particles of PEI were prepared to have surface areas, as shown in Table IV, of about 1.0 to 9.0 square meters per gram as determined by BET ((Brunauer, Emmett, and Teller), surface areas obtained on a Quantasorb BET™ Surface Analyzer (manufactured by Quantachrome, Co.)) surface analysis. Compositions of each were prepared by mixing 4.65 parts of the particles in 50 parts of PR-500 epoxy resin at 60� C. as described in Example 3 and their viscosity profiles were determined by RDA-700. The dissolution temperature, Td, of each composition is given in Table IV.
TABLE IV______________________________________ Surface DissolutionComposition Area (m2 /g) Temp. (�C.) Tdc �C.______________________________________R 1.01 127 153S 2.65 114 138T 2.73 108 131U 3.60 107 133V 4.73 95 112W 8.98 92 115______________________________________
From Table IV, it is to be observed that for the thermoplastic polyetherimide, PEI, that by control of the surface area from about 1.0 to 9 0, the dissolution temperature of the composition was controlled from 127� to 92� C.
The viscosity profile of a 10.0 weight % composition of the particulate thermoplastic polyimide, Durimid™ (available from Rogers Corporation) in PR-500 epoxy resin was obtained by RDA-700. No dissolution temperature was observed; the composition therefore, illustrated a thermosettable composition not included in the invention.
A thermosettable composition of 50 parts of PR-500 epoxy resin and 5.56 parts of conventionally ground polyetherimide thermoplastic resin, having a surface area of 0.3 m2 /g, was prepared as described above and its viscosity profile obtained. No dissolution temperature was observed, the viscosity continued to drop with increasing temperature up to onset of polymerization of the epoxy resin. Prepregs prepared of this composition possessed voids and discontinuities similar to that of epoxy resin without the modifying thermoplastic.
Three thermosettable compositions, X, Y, and Z of PR-500 epoxy resin and polyetherimide (PEI) particles having a surface area of 4.73 m2 /g were prepared by mixing the components at 60� C. using an air stirrer. Compositions X, Y, and Z contained 2.63 parts (5.0%), 4.65 parts (8.5%), and 5.56 parts (10.0%) of PEI, respectively, in 50 parts of PR-500 epoxy resin. Viscosity profile of each composition was obtained and the minimum viscosity observed to be 3.5 poise, 10.35 poise, and 21.22 poise respectively. This illustrated the control of viscosity that was important during the early stages of a processing operation, e.g., prepreg fabrication, that was obtained using compositions of the invention.
______________________________________Td for 5% PEI 95� C.Tdc for 5% PEI 113� C.Td for 81/2% PEI 95� C.Tdc for 81/2% PEI 112� C.Td for 10% PEI 96� C.Tdc for 10% PEI 114______________________________________
A thermosettable resin composition was prepared by mixing 91.5 parts of PR-500 epoxy resin and 8.5 parts of particulate polyetherimide having a surface area of 5.37 m2 /g. The mixing was performed in a planetary mixer at 35� C. under vacuum. The resin composition was further processed into a resin film approximately 66 micrometers thick. The film was laminated with continuous carbon fibers (IM7™ fibers Hercules Co.) using a conventional 30 cm wide prepregging machine (available from California Graphite Machines, Inc.). Sixteen plies of prepreg made by this process were layed-up and cured by a conventional autoclave cycle, to form a void free composite panel having a glass transition temperature of 205� C., useful as a structural component in a machine.
When the procedure of Example 10 was repeated using prepreg that had not been modified with particulate thermoplastic resin, the panel obtained had many voids due to excessive resin flow.
Illustrating the control of the dissolution temperature by plasticizing the thermoplastic particle
Plasticized polyetherimide thermoplastic particles (PEI/DGF) were prepared by dissolving 90 parts PEI and 10 parts by weight of bis[4-(2,3-epoxypropoxy)phenyl]fluorene in 300 parts of dichloromethane, emulsifying in water and coagulating by pouring into methanol. Particles having an average diameter of 3 micrometers and a surface area of 5.40 m2 /g were obtained. Into 50 g of PR-500 epoxy resin at 60� C. were dispersed 4.65 g of these particles and the viscosity profile of the mixture was obtained. A dissolution temperature of 95� C. as compared to 106� C. for the unplasticized polyetherimide particles (Example 3) was obtained.
______________________________________Plasticized Td 95� C. Tdc 117� C.Unplasticized Td 106� C. Tdc 128� C.______________________________________
The data show that the addition of a plasticizer for the thermoplastic particles reduces the dissolution temperature of the particles in a thermosettable resin.
Formulations AA, BB, and CC were prepared, each to contain 50 parts of epoxy resin mixture of 35% bis[4-(2,3-epoxyproproxy)phenyl]fluorene (DGF) and 65% of diglycidyl ether of bisphenol A (DGEBA) and 4.65 parts, respectively, of polysulfone (PS), PEI/DGF (the epoxy plasticized polyetherimide described in Example 11), and polyetherimide PEI (the polyetherimide as used in Example 3) by mixing at 60� C. using an air stirrer. An RDA-700 viscosity profile of each was obtained, each including a dwell period at a temperature about 15� C. below the dissolution temperature. Table V shows the dissolution temperature, the dwell temperature, and the viscosity at the beginning and end of the two hour dwell time.
TABLE V______________________________________ Td Temp. (�C.) Viscosity (poise)Formulation (�C.) of Dwell Initial Final______________________________________AA 86 70 10.8 11.0BB 95 80 4.3 4.5CC 106 90 2.8 2.8______________________________________
The data of Table V show that for compositions of the invention of a thermosettable resin and particles of thermoplastic having a dissolution temperature of 86�, 95�, and 106� C., respectively, can be held at a temperature about 15� C. below the dissolution temperature for at least two hours without an appreciable change in the viscosity of the composition.
A thermosettable composition of PR-500, an aromatic epoxy resin available from 3M, and 8.5% by weight of polybenzimidazole (PBI) particle was prepared by mixing 4.65 parts of Ultrafine PBI (Celanese Corporation) having a surface area of 12.3 m2 /g with 50 parts of PR-500 at 60� C. using an air stirrer. The viscosity profile for this composition showed no evidence of dissolution of PBI. The profile is essentially the same as that obtained for an unmodified PR-500 composition.
Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope of the invention.
|Cited Patent
|Filing date
|Publication date
|Mar 30, 1972
|Jan 8, 1974
|Ciba Geigy Ag
|Reinforced composites
|Apr 4, 1974
|Dec 9, 1975
|Owens Corning Fiberglass Corp
|Molding compounds and method of making same
|Nov 10, 1975
|Sep 13, 1977
|Scm Corporation
|Pigmentable low shrink thermosetting polyesters
|Nov 12, 1976
|Jun 20, 1978
|Owens-Corning Fiberglas Corporation
|Molding compounds
|Apr 26, 1978
|Jun 5, 1979
|Allied Chemical Corporation
|Thermoformable compositions comprising a crosslinked polycyanurate polymer and a thermoplastic polymer
|Dec 15, 1981
|Feb 7, 1984
|Minnesota Mining And Manufacturing Company
|Heat activatable adhesive with improved temperature resistance
|Sep 24, 1982
|May 29, 1984
|Toyo Seikan Kaisha Ltd
|Side seam-coated welded cans and process for preparation thereof
|Jan 24, 1983
|Aug 28, 1984
|Elastomer modified bis-maleimide resin
|May 31, 1983
|Oct 23, 1984
|The B. F. Goodrich Company
|Filler particles coated with reactive liquid polymers in a matrix resin
|Aug 11, 1983
|Jun 18, 1985
|Minnesota Mining And Manufacturing Company
|Curable epoxy compositions and cured resins obtained therefrom
|Aug 1, 1983
|Dec 10, 1985
|American Cyanamid Company
|Curable epoxy resin compositions
|Mar 21, 1986
|May 26, 1987
|Minnesota Mining And Manufacturing Company
|Fast curing epoxy resin compositions
|Feb 9, 1987
|Nov 3, 1987
|Minnesota Mining And Manufacturing Company
|Method for adhering surfaces using fast curing epoxy resin compositions
|Apr 3, 1987
|May 17, 1988
|International Business Machines Corporation
|Fluorine containing dicyanate resins
|Apr 9, 1986
|Oct 25, 1988
|Mitsubishi Gas Chemical Co. Inc.
|Curable thermosetting cyanate ester composition
|Jul 8, 1987
|Feb 14, 1989
|Amoco Corporation
|Cyanate ester with urea latent cure accelerator
|Apr 6, 1988
|Jul 11, 1989
|Minnesota Mining And Manufacturing Company
|Acid catalyzed, toughened epoxy adhesives
|Feb 13, 1989
|Sep 4, 1990
|Lockheed Corporation
|Production of thermoset composites containing thermoplastic fillers
|Dec 15, 1987
|Mar 26, 1991
|The Dexter Corporation
|Toughened prepregs and formulations
|Sep 1, 1983
|May 16, 1984
|The British Petroleum Company p.l.c.
|Epoxy resin composition
|Nov 2, 1987
|May 11, 1988
|Amoco Corporation
|Resin compositions comprising aromatic cyanate esters, polyepoxide compounds and thermplastic polymers and prepreg made therefrom
|Dec 23, 1987
|Jul 20, 1988
|Toray Industries, Inc.
|Highly tough composite materials
|Jul 19, 1988
|Feb 1, 1989
|The Dow Chemical Company
|Rubber-modified cyanate ester resins, their preparation and polytriazines derived therefrom
|Apr 5, 1990
|Oct 17, 1990
|Cytec Technology Corp.
|Toughened thermosetting structural materials
|Feb 12, 1990
|Aug 23, 1990
|Hexcel Corporation
|Toughened resin systems for composite applications
|Aug 10, 1990
|Feb 21, 1991
|Epoxy matrix toughened with polyimide thermoplastic resin
|Chemical Patents Index, Basic Abstracts Journal, Section Ch, Week 8806, Apr. 6, 1988 (Derwent Publications Ltd., London, GB; Class A AN 88 039225(06) and JP A 62 297 316 (Toray Ind. Inc.) Dec. 24, 1987.
|Chemical Patents Index, Basic Abstracts Journal, Section Ch, Week 8806, Apr. 6, 1988 (Derwent Publications Ltd., London, GB; Class A AN 88-039225(06) and JP-A-62 297 316 (Toray Ind. Inc.) Dec. 24, 1987.
|M.T. Blair et al., 33rd Int'l SAMPE Symposium, March 7-10, 1988, "The Touchening Effects of PBI Matrix Resin".
|Citing Patent
|Filing date
|Publication date
|Jul 28, 1993
|Nov 1, 1994
|Kanegafuchi Kagaku Kogyo Kabushiki Kaisha
|Flame-retarded thermosetting resin composition, prepregs and electrical laminates made therefrom
|Sep 13, 1994
|Nov 21, 1995
|International Business Machines Corporation
|Triazine polymer and use thereof
|May 16, 1994
|May 21, 1996
|Ibiden Co., Ltd.
|Adhesives, adhesive layers for electroless plating and printed circuit boards
|Jun 6, 1995
|Jul 16, 1996
|International Business Machines Corporation
|Method of sealing a soldered joint between a semiconductor device and a substrate
|Jul 31, 1992
|Aug 20, 1996
|International Business Machines Corporation
|Modified dicyanate ester resins having enhanced fracture toughness
|Jun 6, 1995
|Apr 22, 1997
|International Business Machines Corporation
|Solder interconnection
|Sep 22, 1995
|Mar 17, 1998
|Minnesota Mining And Manufacturing Company
|Curable epoxy resin compositions with 9,9'-bis(4-aminophenyl)fluorenes as curatives
|Sep 30, 1997
|Nov 30, 1999
|Ibiden Co., Ltd.
|Resin composites and method for producing the same
|Dec 22, 1997
|Dec 28, 1999
|3M Innovative Properties Company
|Prepregs of curable epoxy resin compositions with 9,9-Bis (4-aminophenyl) fluorenes as curatives
|Oct 15, 1999
|Apr 25, 2000
|3M Innovative Properties Company
|Curable epoxy resin compositions, on release liners with 9,9-bis4-aminophenyl) fluorenes as curatives
|Feb 26, 1999
|Sep 26, 2000
|Ibiden Co., Ltd.
|Resin composites and method for producing the same
|Apr 19, 2000
|Jul 24, 2001
|Ibiden Co., Ltd.
|Resin composites and method for producing the same
|Apr 19, 2000
|Sep 25, 2001
|Ibiden Co., Ltd.
|Resin composites and method for producing the same
|Apr 19, 2000
|Oct 23, 2001
|Ibiden Co., Ltd.
|Resin composites and method for producing the same
|Jun 17, 1999
|Apr 30, 2002
|Georgia Tech Research Corporation
|Reworkable high temperature adhesives
|Jun 23, 1999
|Jun 18, 2002
|Schlegel Corporation
|Weatherseal having a contact layer with thermoplastic particles in a thermoset carrier
|Apr 19, 2000
|Sep 17, 2002
|Ibiden Co., Ltd.
|Resin composites and method for producing the same
|Dec 31, 2002
|Jul 4, 2006
|3M Innovative Properties Company
|Drag reduction article and method of use
|Feb 26, 2002
|Nov 28, 2006
|3M Innovative Properties Company
|Protective articles
|Oct 27, 2006
|Oct 27, 2009
|3M Innovative Properties Company
|Protective articles
|Aug 20, 2004
|Jul 27, 2010
|Sakuranomiya Chemical Co., Ltd
|Process for preparing a metal coating material comprising condensation polymerized resin nanoparticles
|Apr 18, 2006
|Nov 16, 2010
|Franklin Industrial Minerals
|Mineral filler composition
|Aug 7, 2007
|Apr 26, 2011
|Toray Industries, Inc.
|Prepreg and carbon fiber reinforced composite materials
|Dec 13, 2011
|Toray Industries, Inc.
|Prepreg and carbon fiber reinforced composite materials
|Jan 31, 2012
|Hexcel Composites, Ltd.
|Composite materials
|Mar 2, 2011
|Mar 20, 2012
|Toray Industries, Inc.
|Prepreg and carbon fiber reinforced composite materials
|Dec 22, 2010
|Sep 11, 2012
|Hexcel Composites, Ltd.
|Composite materials
|Mar 12, 2013
|Toray Industries, Inc.
|Prepreg and carbon fiber reinforced composite materials
|May 26, 2010
|Sep 30, 2014
|Cytec Technology Corp.
|Engineered cross-linked thermoplastic particles for interlaminar toughening
|Aug 5, 2008
|Mar 17, 2015
|Hexcel Composites Limited
|Composite materials
|Dec 20, 2010
|Mar 17, 2015
|Hexcel Composites Limited
|Composite materials
|Oct 9, 2012
|Sep 1, 2015
|X-Card Holdings, Llc
|Information carrying card comprising a cross-linked polymer composition, and method of making the same
|Oct 11, 2012
|Nov 10, 2015
|X-Card Holdings, Llc
|Information carrying card comprising a cross-linked polymer composition, and method of making the same
|Aug 1, 2011
|Dec 29, 2015
|Toray Industries, Inc.
|Prepreg and carbon fiber reinforced composite materials
|Oct 10, 2012
|Mar 1, 2016
|X-Card Holdings, Llc
|Information carrying card comprising a cross-linked polymer composition, and method of making the same
|Jan 30, 2002
|May 30, 2002
|Janes Dennis W.
|Weatherseal having a contact layer with thermoplastic particles in a thermoset carrier
|Feb 26, 2002
|Dec 5, 2002
|Clemens Timothy J.
|Protective articles
|Dec 31, 2002
|Jul 1, 2004
|Dietz Timothy M.
|Drag reduction article and method of use
|May 26, 2006
|Sep 28, 2006
|Coveright Surfaces Holding Gmbh
|Synthetic resin film for laminates and method of producing same
|Jun 28, 2005
|Dec 28, 2006
|Martin Cary J
|Resin compositions with high thermoplatic loading
|Aug 20, 2004
|Dec 28, 2006
|Masao Yamazaki
|Coating material for metal and metallic container coated with the coating material
|Apr 18, 2006
|Nov 15, 2007
|Whitaker Robert H
|Novel mineral filler composition
|Aug 7, 2007
|Jul 15, 2010
|Nobuyuki Arai
|Prepreg and carbon fiber reinforced composite materials
|May 26, 2010
|Dec 2, 2010
|Cytec Technology Corp.
|Engineered cross-linked thermoplastic particles for interlaminar toughening
|Dec 22, 2010
|Apr 21, 2011
|Hexcel Composites, Ltd.
|Composite materials
|Apr 21, 2011
|Hexcel Composites, Ltd.
|Composite materials
|Jun 6, 2009
|May 12, 2011
|Toho Tenax Co., Ltd
|Epoxy resin composition and prepreg using the same
|Jun 23, 2011
|Nobuyuki Arai
|Prepreg and carbon fiber reinforced composite materials
|Jun 23, 2011
|Nobuyuki Arai
|Prepreg and carbon fiber reinforced composite materials
|Sep 8, 2011
|Polytronics Technology Corp.
|Methods for manufacturing insulated heat conductive substrate and insulated heat conductive composite substrate
|May 23, 2006
|Mar 12, 2008
|Hexcel Corporation
|Resin compositions with high thermoplastic loading
|Mar 1, 2002
|Jul 30, 2014
|3M Innovative Properties Company
|Protective Articles
|Aug 20, 2004
|Mar 3, 2005
|Sakuranomiya Chemical Co., Ltd.
|Coating material for metal and metallic container coated with the coating material
|May 27, 2010
|Dec 2, 2010
|Cytec Technology Corp.
|Engineered cross-linked thermoplastic particles interlaminar toughening
|Mar 26, 2013
|Oct 10, 2013
|X-Card Holdings, Llc
|Information carrying card comprising a cross-linked polymer composition, and method of making the same
|Nov 1, 2013
|May 22, 2014
|Cytec Industries Inc.
|Thermoset resin composite materials comprising inter-laminar toughening particles
|U.S. Classification
|525/423, 525/535, 525/426, 525/434, 525/467, 525/445, 525/437, 525/463, 525/438, 525/523
|International Classification
|Cooperative Classification
|European Classification
|Dec 13, 1991
Owner name: MINNESOTA MINING AND MANUFACTURING COMPANY, MINNES
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:PORTELLI, GENE B.;SCHULTZ, WILLIAM J.;BODEN, JOHN T.;AND OTHERS;REEL/FRAME:005954/0278
Effective date: 19911210
|Sep 27, 1994
|Certificate of correction
|Jun 25, 1997
|Fee payment
Year of fee payment: 4
|Jun 27, 2001
|Fee payment
Year of fee payment: 8
|Jul 5, 2005
|Fee payment
Year of fee payment: 12


text:
Season 4, Episode 20 Memphis/Shelby County, Tennessee
First Aired: January 18, 1992
A distraught husband tries to keep his wife from leaving; marijuana is discovered in the car of a family passing through town; and Mississippi officers join in a pursuit when suspects cross the state line.
Next On TVSee all »
Sat Jul 23 5:00pm
CopsSPIKEI'll Watch1881 Watching
Cast & Details See all »
- Premiered: March 11, 1989
- Rating: TV-PG
- Premise: Real-life officers are followed by a camera crew, cinéma-vérité style, in a gritty up-close look at police work and the consequences of crime. The result: one of Fox's longest-running series (it premiered in March 1989). It also spawned a number of police-… (more)
Trending TonightSee all »
Rush Hour9:01 pm | CBSI'll Watch297 Watching
Hell on Wheels9:00 pm | AMCI'll Watch254 Watching
Jail: Big Texas
Jail: Big Texas9:00 pm | SPIKEI'll Watch95 Watching
Watch This
Who Said It: Taylor Swift or Meredith Grey?
The French Connection: A True Account of Cops, Narcotics, and International Conspiracy
By Lyons PressBuy New: $12.84
Cops - 20th Anniversary
By 20th Century FoxBuy New: $20.17
The Revolution Was Televised: The Cops, Crooks, Slingers, and Slayers Who Changed TV Drama Forever
By TouchstoneBuy New: $13.31
Popular Shows
- 1. Orange Is the New Black
- 2. UnReal
- 3. Mr. Robot
- 4. Game of Thrones
- 5. Outlander
- 6. Preacher
- 7. Pretty Little Liars
Popular Movies
Popular Celebrities
- 1. Rami Malek
- 2. Taylor Schilling
- 3. Constance Zimmer
- 4. Emilia Clarke
- 5. Tom Hiddleston
- 6. Kit Harington
- 7. Gina Rodriguez

subset: commoncrawl


text:
The Dow Jones industrial average dropped for the fourth day in five, closing at its lowest level in six weeks, as investors waited for further developments from Washington where political gridlock is bringing the nation closer to a potentially calamitous default. The Standard
The Dow Jones industrial average fell 159.71 points, or 1.1 per cent, to close at 14,776.53.
The S
The Nasdaq composite dropped 75.54 points, or 2 per cent, to 3,694.83.
For the week:
The Dow is down 296.05 points, or 2 per cent.
The S
The Nasdaq is up 112.92 points, or 3 per cent.
For the year so far:
The Dow is up 1,672.39 points, or 12.8 per cent.
The S
The Nasdaq is up 675.32 points, or 22.4 per cent.


text:
Absolute Hotel Limerick, Limerick (county)
- Free WiFi and free parking
Main amenities
- 99 smoke-free guestrooms
- Restaurant
- Breakfast available
- 8 meeting rooms
- In-room childcare
- Terrace
- 24-hour front desk
- Air conditioning
- Daily housekeeping
- Computer station
- Front desk safe
- Laundry service
What's around
- In Medieval Quarter
- King John's Castle (0.3 mi / 0.5 km)
- Hunt Museum (0.3 mi / 0.5 km)
- Thomond Park (1.2 mi / 1.9 km)
- Bunratty Castle and Folk Park (10.5 mi / 16.9 km)
Absolute Hotel Limerick, Limerick (county)
Hotel Info: 866-539-8117from $116
- Superior Room, 1 King Bed
- Superior Twin Triple Room
- Standard Double or Twin Room (Mobile Special)
- Classic Twin Room
- Classic Double Room
- Suite
Also popular with travelers from the USA
At a glance
Key facts
Hotel size
- This hotel has 99 rooms
- This hotel is arranged over 5 floors
- Check-in time starts at 3 PM
- Check-out time is Noon
- Express check-in
Required at check in
- Credit card deposit required
- Government-issued photo ID required
Travelling with others
- Babysitting/childcare *
- Pets not allowed
- Free WiFi in public areas
- Free WiFi and wired Internet access in rooms
- Free self parking (limited)
- Discounted offsite parking
Other information
- Smoke-free property
Nearby Four Star Limerick (county) hotels
In the hotel
- In-room childcare (surcharge)
- Full breakfast daily (surcharge)
- Restaurant
- Room service (during limited hours)
- Number of meeting rooms - 8
- Meeting rooms 8
- Computer station
- 24-hour front desk
- Dry cleaning/laundry service
- Laundry facilities
- Hair salon
- Free newspapers in lobby
- Luggage storage
- Year Built 2007
- Elevator/lift
- Safe-deposit box at front desk
- Terrace
- Accessible bathroom
In the room
- In-room climate control (air conditioning)
- Air conditioning
- Coffee/tea maker
- Iron/ironing board (on request)
- Hypo-allergenic bedding available
- Blackout drapes/curtains
- Premium bedding
- Private bathroom
- Shower only
- Hair dryer
- Pay movies
- Premium TV channels
- Desk
- Free newspaper
- Free WiFi
- Free bottled water
- Daily housekeeping
- In-room safe (laptop compatible)
Top Limerick (county) hotels
Recently reviewed hotels in Limerick (county)
- Shannon Springs HotelFrom
"The staff was very helpful and the room was facility were better than my parents' room at the Park Inn by Radisson for half the price. The staff didn't inform them that there was…"Jun 15, 2016
- St.Patrick's B&BFrom
"This b&b is in a great location, out of the busy downtown area. The Inn keeper recommended a place in Quin, and it was one of the tastiest, reasonably priced establishments we…"Jun 15, 2016
- Bunratty Castle HotelFrom
"The staff at the front could have been a bit more friendly, but they were experiencing some difficulty with computers."Jun 6, 2016
- Carrygerry Country HouseFrom
"Classic elegance beautifully maintained. Great customer service. Had a great dinner the night of our arrival."Jun 6, 2016
Nearby hotels
Special features
DiningAbsolute Bar and Grill - This restaurant serves breakfast, lunch, and dinner. Guests can enjoy drinks at the bar. A children's menu is available.
Absolute Hotel Limerick, Limerick (county)'s small print
Also known as
- Absolute Hotel
- Absolute Hotel Limerick
- Absolute Limerick
- Absolute Limerick Hotel
- Hotel Absolute Limerick
- Limerick Absolute Hotel
- Absolute Hotel And Spa
This hotel will place an authorization upon check-in for the total amount for the stay plus an additional EUR 50 per night. If no credit card is available, a debit card must be presented for full prepayment of the stay; no credit will be available for the room. Cash payments are not accepted. Pre-authorizations will be placed on credit cards prior to arrival once the cancellation period has ended. For more details, please contact the office using the information on the reservation confirmation received after booking.
The name on the credit card used at check-in to pay for incidentals must be the primary name on the guestroom reservation.
Optional extras
Parking is available nearby and costs EUR 5.00 per 24 hours
Full breakfast is offered for an extra charge of EUR 12.50 per person (approximately)
Babysitting/childcare is available for an extra charge
We have included all charges provided to us by this hotel. However, charges can vary, for example, based on length of stay or the room you book.
Is the description of this hotel not correct? Tell us


text:
Old-fashioned Red Devil's Food Cake, left, barely gets a tinge of red from the chemical reaction between acid and alkaline ingredients in a recipe from The Spokesman-Review's Dorothy Dean's Homemakers Service in 1936. Red Velvet Cake was popularized later in a leaflet from 1962 and called for 2 ounces of red food coloring to achieve the deep red color.
You must be logged in to post comments. Please log in here or click the comment box below for options.comments powered by Disqus


text:
Rewrite existing CSS, HTML and JS for single page
This project received 17 bids from talented freelancers with an average bid price of $28 USD.Get free quotes for a project like this
Skills Required
Project Budget$10 - $30 USD
Total Bids17
Project Description
I have taken code from around the web that will allow users to input a URL and it shows them what it looks like on Desktop/Tablet/Mobile views.
I now need someone to make the code obscure to users should anyone check the source files.
I would do this myself, but am short on time. I'd prefer to keep the details and current source confidential, so please contact for more details
Looking to make some money?
- Set your budget and the timeframe
- Outline your proposal
- Get paid for your work
Hire Freelancers who also bid on this project
Looking for work?
Work on projects like this and make money from home!Sign Up Now
- Forbes
- The New York Times
- Time
- Wall Street Journal
- Times Online


text:
(Hint: It's not François Hollande's predilections)
Things are far from quiet on the Western Front
North-south divide produces 'economics of the madhouse'
LONDON, Ont. – The mayor of London, Ont., will be going to trial on fraud charges this spring.
A date of May 26 has been set for the trial of
As the global super-rich buy real estate, the market is 'losing touch with reality'
Cheerleader ticketed for cheering on homecoming weekend
No silver bullet, but a salvo of ideas
A list of things people got stuck in
Victoria Henry on scaling a London landmark, Arctic drilling and getting arrested for a cause
All eyes are on Kate, duchess of Cambridge
Our resident Royals watcher on celebrations of the Queen's birthday
Cards replicate 'sickly sweet' grow-op smell
It hardly fits the city's tolerant, multicultural vision, but white Britons are now the minority in London
Londoners payment benefits may depend on their diet and gym regimen
LONDON, Ont. – Lawyers for an Ontario mayor who is facing criminal charges stemming from his time as a Liberal member of Parliament will appear in court today.
Joe Fontana
Former Liberal MP Joe Fontana, currently the mayor of London, has been charged by the RCMP in connection with a cheque used to pay for his son's wedding reception.
Bully arrests, a sexist scientist, Bob Rae & The Bachelor


text:
Marmot Sawtooth Sleeping bag�170, added Oct/2009, see all Marmot news & reviews
announcement by Marmot
- shivering
- cold aches
- discomfort
- ice-cream headaches
If you are suffering from any of these symptoms this winter then it's time to look at Marmot's cure for the common cold!
Relieve common cold symptoms with our soothing blend or 600 fill power goose down and fast acting classic trapezoidal foot box construction, stretch tricot baffles, down-filled collar and heat bump draft tubes.
Bin the hot water bottle and purchase Marmot's Sawtooth sleeping bag over the counter from any good Marmot stockist. Marmot highly recommends you read the product label before use.
Ingredients include:
- Classic trapezoidal foot box for more foot room
- Heater pocket in foot box for heat packets
- Locking zippers keep the bag from opening up in the middle of the night
- Stretch tricot baffles provide ultimate strength, durability and bag life
- Stuff and storage sack included
- Down-filled collar with easy access draw cord
- Heat bump draft tube
- Nautilus 6-baffle hood 6 chambers of down around head for better down control and fit, hood cord is positioned for easy access
Please read the following before use:
- Weight: 1.304 kgs
- Fill Weight: 623.7 g
- Main Material: 100% Nylon Ripstop AC 1.3 oz/yd
- Main Material: 100% Nylon WR 1.4 oz/yd
- Lining Material: 100% Polyester Dobby WR 2.2 oz/yd
- Insulation Material: 600+ Fill Goose Down
- Internal Length: 183 cm
- Lower Limit: -9.8C EN 13537 Tested
Buy your cure for the common cold over the counter now by visiting any one of the following:
Cotswold Outdoor: Tel: 0844 557 7766 Web: www.cotswoldoutdoor.com
George Fishers: Tel: 017687 72178 Web: www.georgefisheronline.co.uk
Jackson Sports: Tel: 02890 238572 Web: www.jackson-sports.com
The Outdoor Warehouse: Tel: 01479 810175 Web: www.outdoorwarehouse.co.uk
More In This Category
The UKC team recently returned from the annual gear-fest that is OutDoor Friedrichshafen. Below are some video interviews with... Read more
The all-new WindBurner 1.8L Personal Stove System built for 2-3 travelers is the latest addition to the award-winning WindBurner... Read more
Dan Bailey reviews a range of pots, pans, kettles and crockery that fold flat for easy packing. Read more
Made for the US military, MSR has now put their most advanced water purifier on the civilian market. But when not being used by... Read more
Related UKC Forum discussions
|FS: Men's Marmot Headwall... 07:17 Fri
|Found: sleeping bag on MacDui 09:52 Mon
|Winter sleeping bag liner... Jul-16
|Sleeping bag versus duvet? Jul-16
|Marmot cycle tours Jul-16
|Norway summer sleeping bag... Jul-16
|PRODUCT NEWS: Boreal Sendai... Jun-16
|Looking for a 'Cheap'... Jun-16
|List more discussions...
Gear News and Outdoor Industry News at UKC and UKH presents climbing, walking and mountaineering equipment and stories that will be of interest to UKClimbing.com's readers. They are not gear reviews and are provided by companies that advertise with UKClimbing Limited. Please feel free to comment about the stories and products on the associated thread.


text:
Union Pacific CEO Lance Fritz, discusses freight volume levels, and his confidence in coal's "place in electricity generation long-term." » Read More
Check out which companies are making headlines after the bell Tuesday: CSX, Intel, Phillips 66 & more.
After CSX reported record Q3 earnings, the company's CEO Michael Ward, discusses what the move in oil prices means for his business, and steps to ensure safety for oil transportation.
CSX is reporting Q3 EPS of $0.51 on revenue of $3.22 billion, with CNBC's Morgan Brennan.
Stocks rose Monday after last week's rout that came as investors fretted signs of a slowing global economy.
Some of Monday's midday movers:
Some of the names on the move ahead of the open.
In order for things to really improve next week, Cramer thinks several situations bear watching over the weekend.
With a Fed meeting and the Alibaba IPO due next week, Cramer said investors are looking at a rough ride.
It's time for the Lightning Round. Cramer makes the call on viewer favorites.
A lawsuit by Allergan says the unusual arrangement by Valeant Pharmaceuticals and activist investor Bill Ackman amounts to insider trading.
Some of the names on the move ahead of the open.
A partnership between Apple and IBM is among the headlines after the bell Tuesday: Apple, IBM, Intel, Yahoo & more.
CSX president, chairman and CEO Michael Ward discusses "record revenue" for the company and sees good strength in the economy.
Quarterly earnings growth and clues from companies' commentaries will tell whether there really will be a bounce back in growth in the second half.
The "Fast Money" traders share their final trades of the day.
The "Fast Money" traders share their final trades of the day.
Rail cars in a CSX train that derailed in Lynchburg, Virginia are still on fire, the company said.
CNBC's Dominic Chu reports a train owned by CSX has derailed near Lynchburg, Virginia. According to Reuters, 3 to 4 tanker cars have been breached and some crude oil has leaked into the James River.
As the U.S. economy picks up momentum, so are industrial stocks. The recent dip in the market makes this an opportunity for savvy investors.
Some Wall Street pros just refuse to hear what American companies are telling them.


text:
St. Joe Graduation 2014
Photographed by: Tammy Daniels - 06/01/2014
|More Slide Shows...
iBerkshires.com Text Ads
MyCom Fed Credit Union
We Have You Covered. Great Auto and Home Loans. Click or Call For Rates. Pittsfield,MA (413)442-6501www.mycomcu.org
On a Roll Cafe
We have daily homemade soups from fresh stock, but we go the extra mile all meats roasted on site.www.onarollcafeandcatering.com
Top Quality Hardwood. Seasoned, Cut, Split, and Dry. Delivery available. Please Call. (413)822-9723www.whitneysfarm.com


text:
Free personalized radio that
plays the music you love
What A Lonely Way To Start The Summertime
Features of This Trackmellow rock instrumentation
r & b influences
a subtle use of vocal harmony
acoustic rhythm piano
chromatic harmonic structure
a busy horn section
a clear focus on recording studio production
minor key tonality
melodic songwriting
intricate arranging
use of chromatic harmony
These are just a few of the hundreds of attributes cataloged for this track by the Music Genome Project.show more
Similar Tracks
Don't have a Pandora account? Sign up
Already have a Pandora account? Log In


text:
The average salary of a(n) Clinical Psychologist in Grand Prairie, Texas is $102,619.
The average hourly rate of a(n) Clinical Psychologist in Grand Prairie, Texas is $49.34.
The average bonus of a(n) Clinical Psychologist in Grand Prairie, Texas is $3,140.00.
Children's Medical Center
Will maintain clinical research programs. Commitment to clinical research with this population. Works closely with psychologists and treatment teams at lower...View job on Indeed.com
Parkland Health & Hospital System
Must be licensed a Psychologist by the Texas State Board of Examiners of Psychologists. Requires familiarity with Clinical Psychology and competency in basic...View job on Indeed.com
UT Southwestern Medical Center
The position requires a doctorate in rehabilitation or clinical psychology from an accredited university and the candidate to be eligible for Texas licensure....View job on Indeed.com
UT Southwestern Medical Center
Clinical Psychologist – UT Southwestern Medical Center Dallas, Psychology Services at Parkland- Inpatient Psychiatry Unit....View job on Indeed.com
Texas Scottish Rite Hospital for Children
This position involves direct clinical inpatient and outpatient services, including therapy and assessment;...View job on Indeed.com


text:
My 96 eclipse drains the battery after it starts up bout 15-20 min. Ive changed the battery n starter n alternator. Any suggestions. The person who I bought the car from ran all kinds of wires like bootleg. Could it be a stray wire touching another
Thursday, August 11th, 2011 AT 7:51 AM


text:
Joined: 29 August 2005
Posts: 23078
The following 3 member(s) liked the above post:
Humtum25, scinerd, nycsweetie,
Joined: 13 August 2010
Posts: 2556
Joined: 30 December 2008
Posts: 932
Many Many Happy Returns of Dis spcl day.............
The following 1 member(s) liked the above post:
Joined: 08 March 2008
Posts: 11434
Joined: 09 March 2010
Posts: 18590
Many Many Happy Returns of the Day Aishwarya!!
The actress bags a role in the show which will supposedly be that of a ...
The actress shares her Khatron ke Khiladi journey with us..
Disclaimer: All Logos and Pictures of various Channels, Shows, Artistes, Media Houses, Companies, Brands etc. belong to their respective owners, and are used to merely visually identify the Channels, Shows, Companies, Brands, etc. to the viewer. Incase of any issue please contact the webmaster.
Popular Channels :Star Plus | Zee TV | Sony TV | Colors TV | SAB TV | Life OK
Quick Links :Top 100 TV Celebrities | Top 100 Bollywood Celebs | About Us | Contact Us | Advertise | Forum Index


text:
Food & Pharmacy Since 1933
Truly Amazing Amaize Corn is here!
Learn more
Northwest Fresh Magazine
Click to read online
Burger Season is Calling
Check out our meat counter
Join the Haggen team
Apply Online
Give the Gift of Food!
Haggen strives to bring the freshest products to you. Please confirm your preferred store location to view the most relevant pricing and item information.


text:
Jennifer Jason Leigh: People can have so many ill-conceived ideas about me based on the parts that I play. I've had guys, when I've been single, come out of the woodwork to date me and I've found out very quickly that they were expecting some kind of whirlwind, some dramatic crazy person - and that's just not me.
User Score: 75
User Score: 40
User Score: 10
User Score: 6
User Score: 4
User Score: 2


text:
Stryker Completes Pivot Medical Acquisition - Analyst Blog
Stryker Corporation
) has closed its acquisition deal of U.S.-based developer of hip
arthroscopy products, Pivot Medical, Inc., announced last month.
However, stock price fell 1.0% following the revelation of the
closing of the all-cash deal as the acquisition is expected to be
neutral to Stryker's 2014 earnings per share, excluding
acquisition, integration-related and intangible amortization
Pivot, a privately held business, sells products for hip arthroscopy with operating facilities in Sunnyvale, Calif. It specializes in hip arthroscopy procedures treating femoroacetabular impingement syndrome (FAI). Pivot's platform of instruments and implants provide efficient access to and restore mobility of the hip with minimal incisions.
Pivot's offerings are expected to complement Stryker's existing Sports Medicine portfolio and will provide Stryker's customers with more comprehensive solutions to address certain challenges faced during current Sports Medicine procedures.
Pivot is the latest addition to Stryker's acquisition spree. Last month, the company also entered into a definitive agreement to acquire German surgical tools firm, Berchtold Holding.
Berchtold, a privately-held business, is a provider of surgical infrastructure equipment with operating facilities in Germany and the U.S. The deal is also expected to be neutral to Stryker's 2014 earnings per share excluding acquisition, integration-related and intangible amortization charges.
Berchtold's product portfolio comprises surgical tables, equipment booms, and surgical lighting systems committed towards maximizing efficiency and safety in operating rooms and ICUs. Stryker will acquire Berchtold for an enterprise value of $172 million.
The Berchtold acquisition is expected to boost Stryker's fast growing endoscopy division and operating room equipment product portfolio by adding complementary solutions. The deal will allow Stryker to strengthen its portfolio and broaden its hospital product offerings.
In December last month, Stryker completed its acquisition of MAKO Surgical for $1.65 billion. The acquisition of MAKO allowed Stryker to get hold of the latter's advanced robotic arm technology known as Robotic Arm Interactive Orthopedic System, or RIO. The technology helps orthopedic surgeons in performing knee and hip joint replacement surgeries.
In Jan this year, Stryker also announced that it will buy Irvine, Calif.-based Patient Safety Technologies ( PSTX ) for $120 million in order to utilize Patient Safety's device to lessen the risk of surgical sponges being left in patients after surgery. Recently, the company settled a lawsuit over the impending deal where it has agreed to make additional disclosures to appease shareholders.
Stryker currently carries a Zacks Rank #2 (Buy). Other players in the medical products industry which are currently worth a look include Enzymotec Ltd. ( ENZY ) with a Zacks Rank #1 (Strong Buy) and Covidien plc ( COV ) with a Zacks Rank #2 (Buy).
COVIDIEN PLC (COV): Free Stock Analysis Report
ENZYMOTEC LTD (ENZY): Free Stock Analysis Report
PATIENT SAFETY (PSTX): Get Free Report
STRYKER CORP (SYK): Free Stock Analysis Report
To read this article on Zacks.com click here.
Zacks Investment Research


text:
Click here to go to our secure, online ticket box office
Enshrinement 2016 Autograph Session Presented by Panini
Location: Basketball Hall of Fame Museum
Time: 12:30pm (Please arrive at museum store at 12:00pm)
A limited number of tickets to the Enshrinement 2016 Autograph Session Presented by Panini are available. Meet select members from the Class of 2016 and take home a piece of basketball history. Ticket does not include items to be autographed, additional terms and restrictions apply.
Class of 2016 Press Conference Presented by Haggar
Location: Basketball Hall of Fame - Jerry Colangelo "Court of Dreams" - Springfield, MA
Time: 2:00pm - 3:00pm
The Class of 2016 Press Conference will be televised lived on NBA TV and streamed globally throughout the world. The highlight of this press conference is the presentation of the Hall of Fame jackets to each member of the Class of 2016. Come tour the museum on this special day and get your chance to be part of this live televised event. All museum admission will be $35.00 for the day which will include invitation to the press conference.
2016 Family Reunion and Awards Dinner Presented by SCP Auctions
Location: Basketball Hall of Fame - Jerry Colangelo "Court of Dreams" - Springfield, MA
Time: 6:00pm - 9:00pm
The Class of 2016 joins all returning Hall of Famers for an exquisite dinner, preceded by an elegant cocktail reception. Programming for this evening will include recognition of the Class of 2016, a brief forum, presentation of the Mannie Jackson Human Spirit Awards, the John Bunn Lifetime Achievement Award, and the Curt Gowdy Media Awards. Don't miss your opportunity to be surrounded by the game's greats! Space is extremely limited.
2016 Enshrinement Gala VIP Reception
Location: TBD
Time: 4:30pm - 6:30pm
The VIP Gala Reception will feature the Class of 2016, along with their presenters and other returning Hall of Famers. Mingle in style over elegant food and beverage stations. Don't miss your chance to see the Class of 2016 one final time before they give their official acceptance speech and are forever enshrined into basketball history.
Class of 2016 Basketball Hall of Fame Enshrinement Ceremony
Location: Springfield Symphony Hall - Springfield, MA
Time: 6:30pm - 9:30pm
Springfield Symphony Hall plays host to the Hall of Fame Enshrinement Ceremony which is the culmination of the greatest careers the sport of basketball has ever seen and one of the most memorable events on the basketball calendar. Come join the Class of 2016, their Hall of Fame presenters, returning Hall of Famers and industry celebrities as these legends are honored by formally being welcomed into the Basketball Hall of Fame family. This event is televised live on NBA TV and streamed globally throughout the evening. Don't miss your opportunity to be present at one of the greatest events in all of sports.
2016 Induction Celebration
Party Presented by Mohegan Sun
Location: Mohegan Sun - Uncasville, CT
Time: 6:30pm - 9:30pm
The Induction Celebration features an introduction of the entire class, highlighted by a special presentation to the Class of 2016. The reception features skillfully crafted food stations that are guaranteed to satisfy. While mingling with the Class of 2016 and returning Hall of Famers, take a moment to enjoy the live entertainment that will be playing throughout the evening. Don't miss your chance to see the Class of 2016 together, all while enjoying an unforgettable evening at the world famous Mohegan Sun.


text:
Liam Williams, one of three Wales internationals back in the Scarlets starting line-up following their RBS 6 Nations success, and Joe Snyman both scored tries, while fly-half Owen Williams contributed the remaining 14 points from four penalties and a conversion.
Zebre matched Scarlets with two tries of their own through Dries van Schalkwyk and Giovanbattista Venditti but they could not add to those scores as they remained rooted to the foot of the standings following an 18th successive defeat.
The win was Scarlets' 12th of the campaign, but it was not enough to keep them in fourth place as rivals Ospreys edged above them after claiming a seven-try triumph over Newport Gwent Dragons in the later kick-off.
- Sports & Recreation
- Rugby
- Scarlets


text:
Out of Stock
- Earn 1% back on qualifying purchases
- The more you shop, the more your earn
- Use your points for great HobbyTron deals
- Bonus points on special promotions
Ships Tomorrow!
5 Rating (0 Customer Reviews)
Similar Products
Wraith 2.4GHz 4.5CH RC Camera Spy Drone
Save: $95.04 (33%)
Sonic 2.4GHz 4.5CH Live-Feed Video Electric Gimbal RC Drone
Save: $120.04 (38%)
Metal Arrow Hawk 3.5CH RC Helicopter
Save: $45.05 (60%)
Refurbished Fusion 3.5CH RC Helicopter
Save: $60.00 (55%)
Refurbished Hercules Unbreakable 3.5CH RC Helicopter
Save: $76.04 (79%)
Metal Sparrow 3.5CH RC Helicopter (Over 2 Feet Long!)
Save: $140.04 (70%)
Save: $60.05 (71%)
Metal Eclipse 35092 3.5CH RC Helicopter
Save: $100.04 (63%)
World Tech Toys MegaHauler 3.5CH Helicopter And Electric RC Truck IR Combo Pack
Save: $55.00 (61%)
Save: $115.00 (64%)
Refurbished World Tech Toys X9 Extremely Tuff 3CH RTF Electric RC Helicopter
Save: $50.04 (71%)
Refurbished Nano Prowler 2.4GHz 4.5CH RC Drone
Save: $55.04 (65%)
X24 Space Explorer 6-Axis 2.4GHz 4.5CH RC Mini Drone
Save: $25.04 (56%)
Batman v Superman 2CH IR RC Helicopter Bundle
Save: $114.03 (71%)
Hercules Unbreakable 3.5CH RC Helicopter 3-Pack Bundle
Save: $178.02 (62%)
Searching for a small RC Helicopter that is built to pull off the some of sickest stunts imaginable? Then the Nine Eagles Solo Pro 100 Mini 3G 3D Electric RC Helicopter is exactly what you need! This flybarless collective pitch 3D micro RC Helicopter allows you to pull off some amazing 3D acrobatics with high precision and speed. It has smooth flight control and an insane 6 Channel 2.4 GHz transmitter insuring that you can travel far off into the distance and that your signal doesn't get jammed. The transmitter is quite more advanced than most other RC Helicopter transmitters, allowing you to pull off some crazy maneuvers that many other models could never do. This product is Ready to Fly, all you need to do is charge the included 3.7V battery with the included wall charger and get 4 AA batteries for the transmitter and you are good to go. The Nine Eagles Solo Pro 100 Mini 3G 3D Electric RC Helicopter is the natural choice for the daredevil pilot who wants to hear some "Ohhh's" and "Ahhhh's" from the crowd!
- Electric Powered
- 6 CH 2.4 GHz LCD Transmitter
- Programmable 3G Flybarless System
- Ready To Fly
- Nine Eagles Solo Pro 100 Mini 3G 3D Electric RC Helicopter
- 3.7V Rechargeable Battery Pack
- Wall Charger
- Transmitter
- Spare Helicopter Blade
- Length: 9.5 inches
- Wingspan: 9.7 inches
Battery Requirements:
- Vehicle: 3.7V Rechargeable Battery Pack (Included)
- Transmitter: 4 AA Batteries (Not Included)
For questions regarding this product please email our friendly customer service team.
Call our Customer Service at 818-675-9000 if you find a lower price on any of our items we'll match it.*
Need Help? Call our Customer Service Team at 818-675-9000. They can help with any questions you may have.
- Your Stuff
- Your Account
- Order Status
- Rewards Program
- Wish List
- Refer A Friend
- #HobbyTronFan
- Giveaways
- Customer Service
- Contact Us
- Order Status
- Policies
- Testimonitals
- Learn
- Blog
- Videos
- Learning Center
- HobbyTron.com
- Daily Deals
- Coupons
- Affiliate Program
- Wholesale
- Site Map


text:
Capricorn daily horoscope
Someone may be calling you on certain behaviors today, Capricorn. It could be that your aggressive nature rubs someone the wrong way and they simply don't have thick enough skin to take it. You may not even be aware of how your warlike attitude affects those around you. This is a good day to see things from someone else's perspective in order to gain a bit more data on the situation.


text:
Select the store
nearest you to check available inventory*
1 Review(s)
Use for quick, sanitary pick-up and handling of goods from counter to customer or use to separate baked goods. Sold in packs of 1000.
Whether you use a microwave, cook food or to make a sandwich, this is one handy product in home use, bakery or restaurant. There is no one on this planet that couldn't have a use for these. (Posted on 11/30/2008)
Use spaces to separate tags. Use single quotes (') for phrases.
There are no product questions yet.
Ask a question, and give an answer. Help your fellow customer.
* Required Fields
Select the number of stars that reflect your overall item rating
share your opinion with others by writing a detailed review
when writing your review, try to avoid:
What do you like about this item?
What do you dislike about this item?
Would you recommend this product to a friend?
pictures speak a thousand words!
post your youtube video link to show how you style this item
Back to top


text:
I know there are quite a few threads similar to this but I just can't put my finger on what im doing wrong on my code, I am able to get entries into mysql via the iphone simulator, so it is working, but i can't fix the alert priorities and the } else if {'s...
basically its a 4 string registration page, sends the 4 strings of data to my .php file, my php file slots the info into my database. Couple problems:
If there is nothing in any of the 4 fields, and the user clicks the create button, it does give the "missing fields" alert appropriately, however it sends a blank entry to my database, so it's obviously not listening to me when i try tell it "DON'T GO AHEAD IF CRITERIA #1 HAS BEEN FAILED". How can I stop this IBAction from carrying out if there is no text in any of the four fields? (My php file only checks for existing usernames and terminates if it finds a match in my database.)
When a user fills in all 4 fields appropriately, and presses the create button, im getting my "connection to server cannot be established" error which I have set. After having played around for maybe 3 hours with the code, i didnt get anywhere, in fact, i do remember a time where I was getting my profile create success alerts, but that was at a time where my database was ONLY recording blank entries.
Sorry about the wall of text, but ive been working on this for about 10 consecutive hours and not getting very far!!!
Any help would be much appreciated <3
//create a user profile
NSString* name = textFieldName.text;
NSString* username = textFieldUser.text;
NSString* password = textFieldPassword.text;
NSString* email = textFieldEmail.text;
NSString *post =[[NSString alloc] initWithFormat:@"name=%@&username=%@&password=%@&email=%@",name,username,password,email];
NSData *postData = [post dataUsingEncoding:NSASCIIStringEncoding allowLossyConversion:YES];
NSString *serverOutput = [[NSString alloc] initWithData:postData encoding: NSASCIIStringEncoding];
if(([textFieldName.text length]==0) || ([textFieldEmail.text length]==0) || ([textFieldPassword.text length]==0) || ([textFieldUser.text length]==0))
UIAlertView * alert = [[UIAlertView alloc] initWithTitle:@"Missing Field"
message:@"Please fill out all fields."
otherButtonTitles: nil];
[alert show];
[alert release];
} else if ([serverOutput isEqualToString:@"Yes"])
UIAlertView *alertsuccess = [[UIAlertView alloc] initWithTitle:@"Success" message:@"Your profile has been created!"
delegate:self cancelButtonTitle:@"OK" otherButtonTitles:nil, nil];
[alertsuccess show];
[alertsuccess release];
} else if ([serverOutput isEqualToString:@"No"])
UIAlertView *alertsuccess = [[UIAlertView alloc] initWithTitle:@"Error" message:@"The specified username is already taken."
delegate:self cancelButtonTitle:@"OK" otherButtonTitles:nil, nil];
[alertsuccess show];
[alertsuccess release];
} else {
UIAlertView *alertsuccess = [[UIAlertView alloc] initWithTitle:@"Error" message:@"Connection to server cannot be established."
delegate:self cancelButtonTitle:@"OK" otherButtonTitles:nil, nil];
[alertsuccess show];
[alertsuccess release];
NSString *postLength = [NSString stringWithFormat:@"%d", [postData length]];
NSURL *url = [NSURL URLWithString:@"http://mywebsite.com/userlogin.php?"];
NSMutableURLRequest *theRequest = [NSMutableURLRequest requestWithURL:url];
[theRequest setHTTPMethod:@"POST"];
[theRequest setValue:postLength forHTTPHeaderField:@"Content-Length"];
[theRequest setHTTPBody:postData];
NSURLConnection *theConnection = [[NSURLConnection alloc] initWithRequest:theRequest delegate:self];
if( theConnection )
webData = [[NSMutableData data] retain];
-(void)connection:(NSURLConnection *)connection didReceiveResponse:(NSURLResponse *)response
[webData setLength: 0];
-(void)connection:(NSURLConnection *)connection didReceiveData:(NSData *)data
[webData appendData:data];
-(void)connection:(NSURLConnection *)connection didFailWithError:(NSError *)error
[connection release];
[webData release];
-(void)connectionDidFinishLoading:(NSURLConnection *)connection
NSString *loginStatus = [[NSString alloc] initWithBytes: [webData mutableBytes] length:[webData length] encoding:NSUTF8StringEncoding];
[loginStatus release];
[connection release];
[webData release];


text:
|Dante Ariola
|Colin Firth, Emily Blunt
|Supporting actors
|Lucas Hedges, Anne Heche, M. Emmet Walsh, Kristin Lehman, Phillip Troy Linger, Devon Woods, Sterling Beaumon, Natalia Volkodaeva, Autumn Dial, Anthony Reynolds, Holden Hansen, Ron Prather, Jason Benjamin, Daniel Jones, Jack Landry, Sol Miranda, Steve Coulter, David Andrews
|MPAA rating
|R (Restricted)
|Captions and subtitles
|English Details
|Purchase rights
|Stream instantly Details
|Amazon Video (streaming online video)
Mr. Firth is a fine actor and I have seen him perform in number of films which were exceptionally well done. This one was not. It was an utter disappointment. Read morePublished 8 months ago by John A. Leraas
Very disappointed. Couldn't finish watching it. That never happens.Published 11 months ago by DIANA C LYNCH
I bought this movie solely because Colin Firth acted in it. This movie is about two people whose lives are off track and they meet and join forces riding around the country seeking... Read morePublished 13 months ago by HMAIII
Wish I could say differently; but this disjointed story can't be enlivened even with two award-winners as leads. The dialogue is plodding and awkward. Read morePublished 15 months ago by hmn